Non-iridescent film with polymeric particles in primer layer

ABSTRACT

This invention relates to an optically clear film of predominantly thermoplastic polyester base layer and a carbodiimide-crosslinked, polyester and polymethylmethacrylate blend primer layer. The base layer preferably has a particle-free core layer and outer layers containing nonpolyester, organic and/or inorganic particles. The primer layer is preferably applied to the base layer from solution that is organic solvent-free. The primer layer and base layer composite can be laminated with a protective layer of primarily acrylic polymer to form a solar control film. Functional additives, such as UV light blockers, can be present in various layers of the solar control film. Polymethylmethacrylate in the primer, especially in combination with crosslinking by the carbodiimide, provides the acrylic coated polyester base solar control film with notably reduced iridescence. Adhesion between the acrylic layer applied from organic solvent solutions and the polyester layers is durable in moist and warm service conditions.

FIELD OF THE INVENTION

The invention relates to optically clear biaxially oriented polyesterfilm with at least one primer layer, having excellent adhesiveproperties to acrylic coating material over the primer layer even underharsh conditions, such as a high moisture environment. The polyesterfilm coated with an acrylic hard coat, has reduced iridescence due todispersion of particles of certain polyurethane orpolymethylmethacrylate within a primer layer between the polyester andthe acrylic hard coat. The polyester film may have UV blocking andweatherable properties and may be preferably used for window film,display film, outside clear label, outside signage and photo voltaicapplications.

BACKGROUND OF THE INVENTION

A commercially and technically important utility for biaxially orientedpolyester films is to serve as a component of many articles such as foodpackaging, printing media, electrical insulation, optical and the otherindustrial uses. The thermal stability, dimensional stability, chemicalresistance, relative high surface energy, optical clarity as well ascost effectiveness of biaxially oriented polyester films are beneficialfor typical end use applications. Regarding optical clarity, biaxiallyoriented polyster films can be used for instance as a substrate ofoptical products such as window films, display parts, touch screen,eyewear, including visors, goggles, and spectacles, lenses, sunscreens,labels and photovoltaic materials. Typically applications will involveplacing optically clear acrylic coating material onto the biaxiallyoriented polyester films.

Although, biaxially oriented polyester film and acrylic coating each areoptically clear, the composite film of biaxially oriented polyester filmcoated with acrylic materal can have adverse optical properties. Forexample, the film can exhibit excessive iridescence. The refractiveindex (“RI”) of an acrylic coating material can be different from the RIof a biaxially oriented polyester film, e.g. polyethylene terephthalate(PET) film that is about 1.66. The difference between these refractiveindices causes optical interference of light rays reflected from thesurface between the acrylic layer and the polyester layer. Thisinterference produces a rippled iridescent appearance through thespectral reflectance of the acrylic material-coated polyester film.Iridescence on the acrylic material coated polyester film is veryevident under spectral light of fluorescent lamps because such light hasa sharp distribution of luminescence that interferes with the rippledspectral reflectance of the acrylic material coated polyester film.

Iridescence is reduced or does not occur if the film is hazy becauselight is scattered. Hazy film is not desirable for many optically clearend use applications. Furthermore, the use of fluorescent lighting inplace of incandescent lighting is increasing due to energy conservationefforts. Consequently, the iridescence of the acrylic material-coatedpolyester film can distort or block the view through the film or detractfrom the desired aesthetic appearance of the article comprising thefilm. Accordingly, the ability to reduce iridescence is gainingimportance.

Another problem with the acrylic material-coated polyester films isadhesion between layers of acrylic material and the polyester layer. Ingeneral, biaxially oriented polyester film has a highly crystallizedsurface that makes the polyester difficult to adhere to an acrylicmaterial coating layer. To overcome this drawback, a primer layer issometimes used between polyester and acrylic polymer layers to improveadhesion.

Japanese Patent Publication Number JP 2004-299101 of YOKOTA SUNAO etal., entitled “Transparent Laminated Film for Surface Protection” isdirected to a transparent composite film with a 10-250 μm thick baselayer of biaxially stretched polyester and a 3-20 μm thick hard coatlayer of acrylic polymer providing at least 90% light transmission. Thefilm is for laminating to a surface of an article, such as a flat paneldisplay member, a nameplate, a window and the like, to protect thearticle from scratching or other damage.

US patent application 2008/0038539 of Yokota et al. discloses acomposite film having a core layer sandwiched between outer layers toform a base polyester layer. A coating layer containing anti-iridescentmaterial covers one side of the base polyester layer and an acryliccoating is disposed over the anti-iridescent coating layer. US '539discloses the effect achieving anti-iridescence by optimizing RI and thecoating layer thickness to minimize infringement of reflection lightwhich causes ripples of the spectral reflectance.

However, the products disclosed by these references do not fulfill theneeds of modern industries for less or no iridescence, and for morerobust adhesion under very harsh condition such as moisture exposure.The disclosed films above have been found to provide a hard coat withonly moderate adhesion to the base layer, especially after exposure toheat and moisture.

SUMMARY OF THE INVENTION

In one aspect this invention relates to a highly optically clear,composite film having a predominantly thermoplastic polyester base layerand a primer layer of a polyester and polyurethane blend composition.The base layer preferably has an A/B/C layered structure with asubstantially particle-free core layer B of polyester and outer layers Aand C of polyester containing non-polyester, organic and/or inorganicparticles. The primer layer is preferably applied to the base layer fromsolution that is organic solvent-free and is crosslinked using acarbodiimide crosslinking agent. The primer layer and base layercomposite can be laminated with a protective layer of primarily acrylicpolymer, for example to obtain a solar control film. Various layers ofthe composite and solar control films can contain effective amounts offunctional additives, such as UV light blockers. Polyurethane in theprimer, especially in combination with crosslinking by the carbodiimide,provides the acrylic coated polyester base solar control film withnotably reduced iridescence and durable adhesion between polyester andacrylic layers in moist and warm service conditions.

It has also been discovered that polymethylmethacrylate (“PMMA”)particles of preselected particle size in the primer composition inplace of polyurethane is very highly effective to reduce the iridescenceof a PET/primer/acrylic polymer composite.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is an elevation cross section view of a composite film accordingto an embodiment of this invention.

FIG. 2 is an elevation cross section view of a solar control filmincluding the composite film of FIG. 1 and a protective layer accordingto another embodiment of this invention.

FIG. 3 is a graphical plot showing hemispherical reflectance (% R) vswavelength (nm), for a comparative example and for selected operativeexamples described in greater detail, below.

DETAILED DESCRIPTION OF THE INVENTION

A basic embodiment of this invention is understood with reference toFIG. 1 showing a cross section of novel composite film 10. Thiscomposite film includes a base layer 5 and a primer layer 2. The baselayer is preferably formed of three sublayers, namely core layer 6, andouter layers 4 and 8. Each of the core and outer layers is predominantlypolyester and can include other components, such as “UV” (ultravioletlight) blocking additives and particles. In another embodiment shown inFIG. 2, a solar film 20 includes a protective layer 9 primarily ofpreferably an acrylic polymer. The protective layer 9 is positioned onthe composite film in contact with the primer layer 2.

In the present invention, the primer layer contains polymeric binder asa major component of the primer layer. The polymeric binder may beselected from, but not limited to, polyester, acrylic, polyurethane orthe mixture thereof. It is preferred to select a polyester binderbecause its RI is similar to that of the polyester base layer and thusis helpful to reduce iridescence in the manner as described in US2008/0038539. Also the polyester binder is very compatible with the basepolyester layer to provide preferred adhesion, in general. A preferredraw material for the polyester binder is a 30% solids dispersion, in 2%propanol, aqueous solution commercially available under the name Eastek®1200 (Eastman Chemicals Company, Kingsport, Tenn.). This polyester hasinherent viscosity of 0.34-0.42, glass transition temperature (Tg) of63° C. and softening point 65° C.

It now has been discovered that very small polyurethane particles,particularly inversely synthesized aliphatic type polyurethane, in theprimer layer 2 provide excellent iridescence canceling. Without wishingto be bound by a particular theory it is thought that the polyurethaneparticle anti-iridescent component scatters light impinging on the film.The iridescence canceling performance is highly effective. Hence,without significantly increasing haze, iridescence normally observedwith an acrylic polymer coated polyester film is reduced orsubstantially completely prevented. Consequently, use of polyurethaneparticles in the primer layer controls iridescence and maintainsexcellent optical clarity and thus is different from conventionalanti-iridescent techniques described in the prior art such as US2008/0038539.

A traditional approach to reducing iridescence in composite filmutilizes refractive index matching techniques. The refractive indices ofthe acrylic material layer and the base biaxially oriented polyesterfilm layer are distinctly different. The refractive index differencegenerates iridescence, as mentioned above. Selecting a primercomposition having a RI that matches and complements those of the twolayers could reduce iridescence by canceling the effect of disparaterefractive indices.

It is contemplated that low iridescence from the polyurethane accordingto this invention is caused by a light scattering phenomenon (withoutincreasing haze) rather than or in combination with refractive indexmatching. This is remarkable because the polyurethane can be utilized ata particle size and concentration low enough to allow excellent opticalclarity of the overall film yet provide good anti-iridescenceperformance. The implications of this theory include that a polyurethanefine particle dispersion in a primer layer can be utilized to reduceiridescence in a wide variety combinations of base layer and the overcoating layer materials. Moreover, low iridescence can be obtainedwithout constraining the primer layer to have a particular refractiveindex that complements the refractive indices of the other compositefilm layers, although the combination of the refractive index matchingmay be preferred.

The preferred iridescence-reducing component polyurethane particle is aninversely synthesized aliphatic polyurethane. The term “inverselysynthesized aliphatic polyurethane” means that the polyurethane isformed by a process in which (i) non-aromatic organic polyisocyanate andnon-aromatic organic polyol are reacted to form a polyurethane polymer,(ii) a neutralizing agent, such as a tertiary amine, is added to waterto form an aqueous solution, and then (iii) the polyurethane polymer isadded to and dispersed in the aqueous neutralizing agent solution. Apreferred inversely produced polyurethane material is commerciallyavailable under the name Neorez R1010 (DSM NeoResins B.V., Waalwijk,Netherlands). It should be understood that use of inversely synthesizedaliphatic polyurethane particles interrelates successfully with severalimportant performance parameters of optically clear and solar controlfilms. In addition to exhibiting little or no iridescence, these filmsare called upon to have high cohesive strength for durability and to behighly transparent with controlled refractive indices. All of theseproperties can be achieved by these polyurethane particles employed in aprimer layer together with polymeric binder and a carbodiimidecrosslinking agent in proper proportions. The polymeric binder providesstructural integrity and serves as a matrix for the dispersed phase ofpolyurethane particles. The crosslinking agent transforms the binder toa rigid network. If too little binder or crosslinking agent is present,the primer will be too weak to durably hold the protective layer to thebase layer. Delamination can occur. The polyurethane particles cancelundesirable iridescence. If too little inversely synthesized aliphaticpolyurethane particles are present, iridescence can occur. Conversely,if there is too much of binder, polyurethane or crosslinking agent, orthe primer layer is too thick, the film can become excessively hazy andthus unsuitable for optical or solar control film utilities. Thedescription and examples of this disclosure provide guidance forselecting relative amounts of the primer components for successfulpractice of this invention. The artisan of ordinary skill will be ableto adjust proportions of primer components and primer layer thicknessaccording to the principles set forth herein to effectively apply theinvention without undue experimentation.

The desired particle size of the polyurethane particles within theprimer layer is about 1 μm to about 100 μm, preferably about 1 μm toabout 60 μm and more preferably about 1 μm to about 25 μm. If theparticle size is larger than 100 μm, the coated film surface can developa grainy appearance. Additionally, the haze value can exceed the lessthan 3% desired limit for the coated polyester film (i.e., the baselayer/primer/acrylic polymer layer composite), thereby reducing theoptical clarity. If the particle size is smaller than 1 μm, theanti-iridescing properties may not be achieved.

The content of the polyurethane particles in the primer layer can be atleast about 0.2 wt % preferably at least about 0.25 wt %, and morepreferably about 0.3 wt %. If the content is less than about 0.2 wt %there may not be enough particles to effectively reduce or eliminateiridescence. There can be at most about 2.5 wt % polyurethane particlesin the primer layer, preferably at most about 2 wt %, and morepreferably at most about 1.5 wt %. If the content is more than about 2.5wt %, the coated film surface may exceed a less than 3% haze value,thereby reducing optical clarity. The urethane particles are preferablyuniformly dispersed within the primer layer. The primer layer should beof a consistent dry coating weight and thickness with adequateunagglomerated dispersed particles to sufficiently provide an opticallyclear coating with a haze value. Primer layer-coated base layer (i.e.,without an acrylic polymer hard coat layer) of this invention has a hazevalue of less than 4%. The preferred thickness of the primer layer isabout 0.03 to 0.15 μm, more preferably, 0.07 to 0.12 μm. If thethickness is less than 0.03 μm, the desired adhesiveness andanti-iridescence effect may not be achieved. If the thickness is morethan 0.15 μm, then presence of the primer can detract from overalloptical clarity and the desired anti-iridescence effect may not beachieved.

As another embodiment of this invention, great preference is given tostrengthening the primer layer and the bond between polyester film layerand the acrylic polymer layer by crosslinking the primer layer.Crosslinking strengthens the primer layer by forming the polymericbinder component of the primer layer into a permanent, rigid, networkstructure. It also produces chemical links between the polymeric binderand the polyester base layer. Crosslinking can be accomplished duringand/or after drying solvent from the wet primer layer. Typically acrosslinking agent is added to the primer composition to catalyze thereaction. Many conventional crosslinking agents for reactingpolyurethane and polyester may be used, such as carbodiimide, melamine,aziridine, glyoxal, oxazoline and mixtures thereof.

It has been found that a carbodiimide crosslinking agent providesexcellent adhesive strength while very effectively preserving theanti-iridescence property afforded by the polyurethane/polyester binderblend. Carbodiimides have the chemical formula R₁N═C═NR₂ in which R₁ andR₂ are hydrogen or hydrocarbon radicals. Additional benefits of usingcarbdimide crosslinker include improved adhesive bonding of film layers,useful potlife, low toxicity, improved chemical resistance andcrosslinking at ambient conditions. A preferred carbodiimidecrosslinking agent is Solucote® XL1 (DSM NeoResins B.V., Waalwijk,Netherlands). Preferably the crosslinking agent is added to the primercoating liquid and mixed to uniform concentration. The preferred contentof the crosslinking agent in the primer layer is about 1 wt % to 5 wt %,more preferably, about 2 to 3 wt %. If the content is less than 1 wt %,the organic solvent resistance properties, the inorganic solventresistance properties and the required adhesive strength of the primerlayer will not be achieved. If the content is more than 5 wt %,excessive crosslinking can produce haze value of the base layer/primerlayer film greater than 4%, thereby reducing optical clarity.

Inversely synthesized aliphatic polyurethane dispersion and thecrosslinking agent are mixed with the polymeric binder dispersion inappropriate preselected ratios to form a primer coating liquid. Thecoating liquid can be applied to a surface of the base layer byconventional coating methods such as dip coating, doctoring, spraying,rod coating and the like. Rod coating is preferred. Followingapplication, the primer coating liquid is dried by heating and lowhumidity ventilation to remove liquid dispersing medium (mainly water),and leave a solid content of the primer layer on the base polyesterlayer. Such coating processes can be done after the biaxially orientedpolyester film is made, or continuously (i.e., in line) with thebiaxially oriented polyester film fabrication. The in line method ispreferred to reduce the number of steps and cost of coating.

Examples of polyester suitable to form the base of the biaxiallyoriented polyester film are, polyethylene terephthalate (PET),polyethylene naphthalate (PEN), polybutylene terephthalate (PBT),polyethylene isophthalate (IPET) and blends or co-polymers thereof. Apreferred polyester is PET because of its good balance of cost andperformance.

The base layer of biaxially oriented polyester film may have a monolayer structure or a multi layer structure such as A/B, A/B/A or A/B/C.A/B/A or A/B/C structures are preferred in which wherein the core layerB is a polymer layer substantially free of particles and layers A and Ceach independently can contain organic and/or inorganic particles. Corelayer B should contain no particles to achieve the preferred opticalclarity of at most about 3% haze value and more preferably at most 2%.The outer layers A and C may have desired slip agents such as organicand/or inorganic particles, as disclosed in US patent application2008/0038539 hereby incorporated herein.

The biaxially oriented polyester film generally has a thickness of from1 to 500 μm, preferably from 5 to 350 μm. A film thickness of 10 to 50μm may be preferred for some applications, such as for solar window filmuse.

The biaxially oriented polyester film can be produced by anyconventional method, such as sequential stretching or simultaneousstretching. In an example of the fabrication process, raw materialpolyester pellets and additives are fed to a melt processor, such as amixing extruder. The molten material, including the additives, isextruded through a slot die and quenched on a chill roll, in the form ofa substantively amorphous film. The film may then be reheated andstretched longitudinally and transversely or transversely andlongitudinally, or longitudinally, transversely, and againlongitudinally and/or transversely. Temperatures during stretching aregenerally above the Tg of the film polymer by about 10 to 60° C.Preferably, the longitudinal stretching ratio is from 2 to 6, morepreferably from 3 to 4.5. Preferably, the transverse stretching ratio isfrom 2 to 5, more preferably from 3 to 4.5. Preferably, any secondlongitudinal or transverse stretching is carried out at a ratio of from1.1 to 5. The first longitudinal stretching may also be carried out atthe same time as the transverse stretching (simultaneous stretching).Heat setting of the film may follow at an oven temperature of about 180to 260° C., preferably about 220° C. to 250° C. The film may then becooled and wound up.

The biaxially oriented polyester film may contain other additives suchas, but not limited to, UV stabilizer, hydrolysis resistant agent,optical brightener, frame retardant agent, anti-oxidation agent.Especially for outdoor applications such as solar window film or photovoltaic application, it is preferable that the polyester film containsUV stabilizer to protect the film itself and/or protect article behindthe film from UV light. Various terms such as “UV light blocker” “UVblocking additive”, “UV stabilizer”, “UV absorber”, “UV agent” and thelike used herein are to be construed interchangeably as referring tocomponents included in the base layer to control the effect ofultraviolet light incident thereon.

Preferred UV absorbers include 2-hydroxybenzotriazoles, benzoxazinonesand the triazines. A more preferred UV absorber is2,4-bis-biphenyl-6-[2-hydroxy-4-(2-ethyl-hexyloxy)phenyl]-1,3,5-triazinein terms of the weatherability and UV resistance performance. Thecontent of UV absorber may be 0.1 to 2 wt. %. Less than 0.1 wt. % is notenough to be effective, more than 2 wt. % may increase haze, yellowcolor, affect the mechanical properties of the film, and may createprocessing issues such as generating undesirable gaseous byproducts andcausing migration to the surface (i.e., “blooming”) of the UV absorber.Preferably, the polyester film includes 0.1 to 2 wt. % UV absorber; morepreferably in the range of 0.5 to 1.5%.

The biaxially oriented polyester film with primer of this invention canbe used as a substrate on which is deposited a coating of acrylicpolymer as mentioned above and seen in FIG. 2. The acrylic polymer layeris preferred to be optically clear and primarily to provide a hard,strong, impact resistant barrier against physical and chemical attackfrom environmental conditions to which the desired application of thisinvention can be exposed in service. That is, such protective layerreduces damage to the film from scratching, denting, moisture,atmospheric-borne contaminants, dirt and permits wash-and-wipe cleaningof the exposed film surface. The preferred thickness of the acrylicpolymer layer is 2 to 5 μm. Coating layer thickness exceeding 5 μm canadversely affect the refractive index and cause iridescence. If thethickness is less than 2 μm, the chemical resistance properties of theacrylic polymer layer can be diminished.

Acrylic polymers for the protective layer of this invention have repeatunits that are derivatives of acrylic acid or substituted acrylic acid.That is, the acrylic polymer is a polymer comprising polymerized unitsof the following formula (I)

(I)

in which X═H, for an acrylic acid derivative, or an alkyl group for analkyl acrylic acid derivative, such as CH₃ for a methacrylic acidderivative. Typically R is an alkyl group, a glycidyl group or ahydroxyalkyl group. Representative acrylic polymers include polymethylmethacrylate, polyethyl methacrylate, polybutyl methacrylate,polyglycidyl methacrylate, polyhydroxyethyl methacrylate, polymethylacrylate, polyethyl acrylate, polybutyl acrylate, polyglycidyl acrylate,polyhydroxyethyl acrylate and mixtures of these. A protective layer ofpredominantly acrylic polymer typically has a refractive index of atmost about 1.54, and frequently about 1.48 to about 1.54.

The acrylic polymer layer can include functional additives for specificpurposes. Typical additives include antioxidants, impact resistancemodifiers, surfactants, light blocking additives and the like.Preferably, the acrylic layer for the desired application such as solarcontrol films contain light blocking additives, particularly UV lightblocking materials. The additives are usually present in minorquantities to avoid degrading optical clarity of the acrylic polymerlayer. Typically the acrylic polymer layer contains a total of less thanabout 1 wt % of additives.

Frequently, coated polyester films are placed on products to provide asolar control function by blocking, absorbing and/or otherwise resistingthe transmission of selective wavelengths of light. These phenomena aresometimes hereinafter collectively referred to as “light blocking”.Ultraviolet light blocking is a significant utility for coated polyesterbase solar control films. PET, which is a most desired polyester, alonedoes not resist transmission of ultraviolet (“UV”) light very well. UVlight blocking is typically improved by placing a coat of an effectiveUV light blocking material on a PET core layer of a composite film. Anexample of such a material is a polymeric coating, for example, a hardcoat such as an acrylic polymer that contains a uniformly dispersed UVlight blocking composition. The hard coat also physically protects thePET base layer with enhanced impact resistance, abrasion resistance andlike properties that lower the risk of damage from denting, scratchingand similar other environmental assaults.

In one embodiment of the invention, the acrylic polymer layer includesUV light blocking materials. In that case, the acrylic polymer layergenerally comprises greater than about 60 wt. %, preferably greater thanabout 80 wt. %, more preferably, greater than about 95 wt. %, and mostpreferably greater than about 98 wt. % of an acrylic polymer and 0 toabout 2 wt. % preferably about 0.05-1 wt. %, more preferably about0.1-0.5 wt. %, and most preferably about 0.2-0.4 wt. % of ultravioletlight blocking component.

The acrylic polymer can be applied to the primer layer from a solutionof the acrylic polymer dissolved in organic solvent. Although theorganic solvent is substantially completely removed from the acrylicpolymer after lamination, trace amounts of solvent can remain in theacrylic polymer layer. By “trace amounts” is meant a minute amount verymuch less than 1 wt %, and barely detectible by rudimentary chemicalanalytical methods. Not uncommonly, the compositions in the primer layerare soluble in organic media. Over time, the very slight but finiteresidual solvent in adjacent acrylic polymer layer can weaken the primerlayer. After exposure to heat and moisture under environmental serviceconditions, cracking and flaking off of the weakened acrylic polymerlayer can occur. A system for adhering acrylic polymer layer appliedfrom organic solvent media onto optically clear solar control films ismuch needed in the industry. Therefore, superior organic solventresistance of the primer layer is also desired and is achieved bycrosslinking agent mentioned above.

The acrylic polymer layer can be laminated to the biaxially orientedpolyester film by various known methods. The term “laminate” is usedherein to mean the generic permanent joining of layers to form acomposite structure and is not limited to any specific method. Forexample, the acrylic polymer layer can be preformed as a sheet andlaminated onto the primer layer using heat and pressure. Acrylic polymercan also be extruded onto the primer layer. Preferably, the acrylicpolymer can be deposited onto the primer layer from a solution. Examplesof solution application methods include doctoring, spraying, painting,dipping, and rod coating techniques. Following application of solution,the solvent is removed by conventional techniques such as heat and/orvacuum treatments. A preferred material for making the acrylic polymerlayer of this invention is an acrylic polymer with a UV cure initiatorsolution in methyl ethyl ketone and isopropyl alcohol solvent. The cureinitiator is one which can be activated by exposure to UV radiation.

Ideally, all of the solvent is removed to leave a dry, e.g. hard coat ofthe acrylic polymer for the solar control film or display film such astouch screen. After the solvent removal step, it is not unusual fortrace amount of the solvent to remain in the seemingly dry acrylicpolymer layer. The primer according to this invention can withstand thesolubilizing effect of the presence of such trace residual solvent. Itis thus able to create a durable and strong bond between the acrylicpolymer layer and the polyester base layer. Consequently, the acrylicpolymer layer will resist cracking, chipping, flaking and peeling fromthe base layer for extended duration.

Among the contemplated embodiments of this invention are included thefollowing.

1. Optically clear biaxially oriented polyester film comprising ananti-iridescent primer layer comprising, (A) polymeric binder as a majorcomponent of the primer layer, (B) 0.1-1.5 wt. % of inverselysynthesized aliphatic polyurethane particle as iridescent reducingcomponent, and (C) at least one crosslinking agent, wherein, the haze ofthe polyester film is 4% or less.

2. The optically clear biaxially oriented polyester film of contemplatedembodiment 1. wherein the polymeric binder is polyester.

3. The optically clear biaxially oriented polyester film of contemplatedembodiment 1. wherein thickness of the primer layer is 0.03-0.15micrometer.

4. The optically clear biaxially oriented polyester film of contemplatedembodiment 1. wherein the crosslinking agent is selected fromcarbodiimide, melamine, aziridine, glyoxal, oxazoline or mixturethereof.

5. The optically clear biaxially oriented polyester film of contemplatedembodiment 1. wherein the crosslinking agent is carbodiimide.

6. The optically clear biaxially oriented polyester film of contemplatedembodiment 1. which further comprises at least one UV absorber.

7. The optically clear biaxially oriented polyester film of contemplatedembodiment 6. wherein the UV absorber is selected from2-hydroxybenzotriazoles, benzoxazinones, triazines and mixture thereof.

8. The optically clear biaxially oriented polyester film of contemplatedembodiment 6. wherein the UV absorber is2,4-bis-biphenyl-6-[2-hydroxy-4-(2-ethyl-hexyloxy)phenyl]-1,3,5-triazine.

9. The optically clear biaxially oriented polyester film of contemplatedembodiment 1. for a window film, optical, display, label or photovoltaic application.

In another embodiment, certain polymethyl methacrylate (“PMMA”)particles can be dispersed within the primer layer in place ofpolyurethane particles. Polyester film having PMMA particles in theprimer layer has been found to have generally equivalent or better filmquality and typically superior iridescence-reducing performance thanthat of film with polyurethane particles.

It has been discovered that dispersing within the primer layer, highlycrosslinked PMMA particles of a particular particle size range gives alow haze, oriented polyester film with secure and durable bonding to anacrylic polymer protective coating and excellent iridescense canceling,With differences now being explained, the amount, and the methods andconditions for incorporating the PMMA into the primer layer aregenerally the same as for polyurethane particles as previouslydescribed.

Preference is given to using spherical PMMA particles. Particlediameters that are suitable in this invention are in the micron rangeand are sometimes referred to herein as “microspheres”. Hollowmicrospheres can be used, however, solid PMMA microspheres arepreferred. The nominal particle size of the PMMA is generally diameterof about 1 μm-10 μm, preferably about 2 μm-8 μm, and more preferablyabout 2 μm-5 μm. Moreover, the particle size distribution of the PMMA ispreferably narrow. Typically greater than 50 wt. % and preferablygreater than 80 wt. % of the PMMA particles have a diameter within arange of about +4 μm to −4 μm of the median particle size, morepreferably within about +2 μm to −2 μm of the median particle size, andmost preferably within about +1 μm to =1 μm of the median particle size.Because the particle size distribution of the PMMA is so narrow, and theparticles are so small, it is possible to provide a highly uniform lightscattering effect across the extent of the film such that negation ofiridescence is uniform effective over broad areas. It is also possibleto control the degree of iridescence canceling while maintainingexcellent optical clarity (i.e., low haze).

Preferred PMMA particles are commercially available under the nameTechpolymer SSX (Sekisui Plastics Co., Tokyo, Japan). This material isunderstood to be a cross-linked polymethylmethacrylate in sphericalparticle form with small particle size distributions. Thischaracteristic makes them well-suited for applications having uniformcoating thickness and surface coverage specifications. In contrast,inversely produced polyurethane particles suitable for use in thisinvention as described above can have slightly more variable particlesize distribution. Particle size variability over the area of the primerlayer can produce subtle iridescent effects. Use of PMMA particlesallows greater control over uniformity of particle size within theprimer layer. While polyurethane particles as set out above can achievegood quality optical films with reduced iridescence, PMMA particles inthe primer layer provide more consistent iridescence reduction.

Additionally, the PMMA particles preferred for use in this inventionprovide a smaller particle size than the preferred polyurethaneparticles in the range of at most about 60 μm nominal particle size.Smaller particle size coupled with precise particle size distribution ofPMMA particles contributes to lower haze across the primer coated PETweb.

It is contemplated that low iridescence from the PMMA according to thisinvention is caused by a light scattering phenomenon (without increasinghaze) rather than or in combination with refractive index matching. Thisis remarkable because the PMMA can be utilized at a particle size andconcentration low enough to allow excellent optical clarity of theoverall film yet provide good anti-iridescence performance. Theimplications of this theory includes that a PMMA particle dispersion ina primer layer can be utilized to reduce iridescence in a wide varietycombinations of base layer and the over coating layer materials.Moreover, low iridescence can be obtained without constraining theprimer layer to have a particular refractive index that complements therefractive indices of the other composite film layers, although thecombination of the refractive index matching may be employed.

It should be understood that use of PMMA particles also influencesseveral important performance parameters of optically clear and solarcontrol films in addition to exhibiting little or no iridescence.Optically clear, solar control films are called upon to have highcohesive strength for durability and to be highly transparent withcontrolled refractive indices. All of these properties can be achievedby these PMMA particles employed in a primer layer together withpolymeric binder and a carbodiimide crosslinking agent in properproportions. The polymeric binder provides structural integrity andserves as a matrix for the dispersed PMMA particles. The crosslinkingagent transforms the binder to a rigid network. If too little binder orcrosslinking agent is present, the primer will be too weak to durablyhold the protective layer to the base layer. Delamination can occur. ThePMMA particles cancel undesirable iridescence. If too little PMMAparticles are present, iridescence can occur. Conversely, if there istoo much of binder, PMMA or crosslinking agent, or the primer layer istoo thick, the film can become excessively hazy and thus unsuitable foroptical or solar control film utilities. The description and examples ofthis disclosure provide guidance for selecting relative amounts of theprimer components for successful practice of this invention. The artisanof ordinary skill will be able to adjust proportions of primercomponents and primer layer thickness according to the principles setforth herein to effectively apply the invention without undueexperimentation.

The content of the PMMA particles in the primer layer can be at leastabout 0.2 wt % preferably at least about 0.25 wt %, and more preferablyabout 0.3 wt %. If the content is less than about 0.2 wt % there may notbe enough particles to effectively reduce or eliminate iridescence.There can be at most about 2.5 wt % polyurethane particles in the primerlayer, preferably at most about 2 wt %, and more preferably at mostabout 1.5 wt %. If the content is more than about 2.5 wt %, the coatedfilm surface may exceed a less than 3% haze value, thereby reducingoptical clarity. The PMMA particles are preferably uniformly dispersedwithin the primer layer.

This invention will be better understood with reference to the followingexamples, which are intended to illustrate specific embodiments withinthe overall scope of the invention.

Optically clear biaxially oriented polyester film comprising ananti-iridescent primer layer comprising, (A) polymeric binder as a majorcomponent of the primer layer, (B) 0.1-1.5 wt. % of PMMA particles (C)

Test Methods

Haze: Haze of films was measured according to ASTM D1003 that determinesthe percent of transmitted light scattered at more than 2.5° from theincident light. A suitable instrument to measure haze is GARDNERHAZE-GARD PLUS No. 4725 hazemeter (BYK-Gardner USA). A haze value of 3%or less is considered acceptable, and 2% or less is preferred.

Iridescent appearance test: Samples of primer layer-coated base layercomposite films were coated with an acrylic polymer layer. A solution ofacrylic polymer composition with a UV cure initiator in methyl ethylketone was drawn onto the composite film sample with a No. 2.5 mayercoating rod. The solution coated composite film was passed at a rate of0.25 m/s (50 ft/min.) through a field of ultraviolet light radiation of620,000 Watts/m² (400 Watts per square inch) to cure and therebysolidify the acrylic polymer composition. The coated film was taped to ablack & white lanetta card (9A). Then the surface of the hard coatingwas visually inspected under fluorescent lamp illumination and ratedaccording to the scale below.

-   -   Rating 1 (Good): No iridescence observed.    -   Rating 2 (Acceptable): Weak iridescence observed.    -   Rating 3 (Unacceptable): Strong iridescence observed.

Acrylic polymer layer (hard coat) adhesion test (Spray Test): A 12.7cm×25.4 cm sample of composite film coated with an acrylic polymer layeras described in the Anti-Iridescent Appearance test method, above, wasrolled up in a cylinder of approximately 2.5 cm diameter and securedwith a paper clip. The rolled up film was exposed to temperature of 66°C. (150° F.) for 5 minutes. Thereafter the cylinder was unrolled and thesurface of the film was visually inspected and rated according to thescale below.

Rating 1 (Good): No discoloration and no separation of acrylic polymerlayer from composite film observed

Rating 2 (Acceptable): Discoloration but no separation of acrylicpolymer layer from composite film observed

Rating 3 (Unacceptable): Discoloration and separation of acrylic polymerlayer from composite film observed

Acrylic polymer layer (hard coat) adhesion test (Boil Test): A 12.7cm×25.4 cm sample of composite film was coated with an acrylic polymerlayer as described in the Anti-Iridescent Appearance test method, above.The acrylic polymer layer-coated sample was submerged in boiling water(100° C.) for 5 minutes. Thereafter the surface of the film was visuallyinspected and rated according to the same scale as in the Spray Test forAcrylic polymer layer adhesion.

Acrylic polymer layer (hard coat) adhesion test (Tape Test):

A 12.7 cm×25.4 cm sample of composite film was coated with an acrylicpolymer layer as described in the Anti-Iridescent Appearance testmethod, above. The acrylic polymer layer surface of the sample waspressed against Scotch Brand 810 adhesive tape to adhere the sample tothe tape. The tape was peeled away rapidly from the tape in directionsperpendicular and parallel to the tape. The sample and tape werevisually inspected for transfer of hard coat acrylic polymer layer tothe tape. The sample failed the test if any of the acrylic polymer layertransferred to the tape.

EXAMPLES

This invention is now illustrated by examples of certain representativeembodiments thereof, wherein all parts, proportions and percentages areby weight unless otherwise indicated. All units of weight and measurenot originally obtained in SI units have been converted to SI units.

Comparative Example 1

Making biaxially oriented polyester film with a primer layer (in linecoating method): Four masterbatch compositions, MB-A through MB-D, ofadditives were prepared by individually blending additive componentswith polyethylene terephthalate in the proportions shown in Table 1.MB-A, MB-B and MB-C were produced by adding the additive components tothe reaction mass during polymerization of the PET. After synthesis, thePET with additive masterbatch compositions were pelletized. MB-D wasmade by charging the additive with PET pellets (0.65 inherent viscosity)to a twin screw extruder in which the masterbatch composition was meltblended and then pelletized.

TABLE 1 Average additive Additive particle size Concentration Additive(μm) (wt %) MB-A CaCO₃ 1.1 1.0 MB-B AlO₂ 0.1 1.5 MB-C SiO₂ 2.0 1.0 MB-DUVA(*) Not applicable* 20 *ultraviolet light absorber2,4-bis-biphenyl-6-[2-hydroxy-4-(2-ethyl-hexyloxy)phenyl]-1,3,5-triazine

An outer layer composition for a polyester base layer film was made bymixing the masterbatch pellets with PET pellets of inherent viscosity0.6 in the proportions shown in Table 2. The combination of pellets wasdried to less than 100 ppm moisture content then melt-blended in anextruder.

TABLE 2 Component (wt %) PET 65 MB-A 22 MB-B  7 MB-C  2 MB-D  4

A core layer was formed by mixing 4 wt. % of MB-D pellets and 96 wt. %PET (inherent viscosity 0.65) pellets, drying the mixture to less than100 ppm moisture content, then melt-blending the dried pellet mixture inan extruder. The outer layer and core layer melt streams were thencontinuously co-extruded at a temperature of 285° C. through arectangular joining zone to form an A/B/A multi-layered melt structure.The multi-layered melt curtain was quenched on a casting drum at 20° C.to form a base layer film. The film was oriented in the machinedirection by stretching to 3.3 times original length at 95° C. with aroller stretcher.

Formulation of the Primer Layer Composition:

A liquid primer composition was formed by combining and blending touniform composition 19.3 parts weight per hundred (“pph”) of a polyesterbinder dispersion, 0.04 pph of a leveling surfactant, 0.08 pph of anantifoam/leveling surfactant, 0.14 pph of an aqueous silica particledispersion, and 2.62 pph of an aqueous crosslinking agent dispersionwith 76.7 pph deionized water. The polyester binder dispersion was a 30wt % solids polyester particle dispersion in 2% propanol, aqueoussolution (Eastek® 1200, Eastman Chemicals Company, Kingsport, Tenn.).The leveling surfactant was an ethoxylated acetylenic diol (Surfonyl440), and the antifoam/leveling surfactant was an ethoxylated acetylenicdiol (Surfonyl 420). The silica particle dispersion was a 20 wt %aqueous dispersion of synthetic amorphous silica particles (Grace 703A,W. R. Grace Co.). The crosslinking agent was a 45 wt % aqueousdispersion of polycarbodiimide (Solucote XL1, (DSM NeoResins B.V.,Waalwijk, Netherlands).

The liquid primer composition was coated with a Mayer rod coater ontoone side of the base layer film. The primer solution was deposited at arate of about 1.4 g/m² of base layer area that was calculated aseffective to produce a primer layer of basis weight of 0.10 g/m², 0.1 μmthickness and 97.9 wt. % crosslinked polyester after drying. The wetcoated film was transported through an oven, preheated at 110° C., andoriented in the transverse direction to 4.0 times original width at 110°C. The composite film was heat-set at 236° C. and relaxed (5%) using achain driven stretcher. The completed film was then wound up. Thebiaxially oriented polyester film had an A/B/A thickness of 1.5/47/1.5μm. The film was aged seven days at ambient temperature for fullcrosslinking to occur.

Application of an acrylic polymer layer on the primed polyestercomposite film, above:

A methyl ethyl ketone (MEK) based, acrylic hard coat containing a UVcure initiator was drawn onto the primed surface of the substratepolyester composite film above with a size No. 2.5 Mayer coating rod.The solution coated composite film was passed at a rate of 0.25 m/s (50ft/min.) through a field of ultraviolet light radiation of 620,000Watts/m² (400 Watts per square inch). The radiation exposure caused thecrosslinking agent to crosslink the polyester binder while volatizingthe MEK from the solution to produce an acrylic polymer coated polyesterfilm (having a dry hard coat of acrylic polymer laminated onto the basepolyester film above).

Samples of the above coated film were subjected to adhesion, haze andanti-iridescence appearance testing. Analytical results are presented inTable 3, below. The product did not meet low iridescence specification.

Example 2

The procedure of Comparative Example 1 was repeated except that theliquid mixture composition for the primer layer consisted of 19.267 pphpolyester primer dispersion, 0.04 pph of leveling surfactant, 0.081 pphof antifoam/leveling surfactant, 0.144 pph of aqueous silica particledispersion, 2.615 pph of aqueous crosslinking agent dispersion and 0.329pph aqueous polyurethane particle dispersion combined with 76.455 pphdeionized water. The aqueous polyurethane dispersion was a 32 wt %solids dispersion of particles less than about 100 μm size of inverselysynthesized aliphatic polyurethane (Neorez R1010, DSM NeoResins B.V.,Waalwijk, Netherlands). The primer layer drying conditions were same asin Comparative Example 1. The dry primer layer basis weight was againabout 0.10 g/m² and dry primer layer thickness was about 0.1 μm.Composition of the dry primer layer was about 96.5 wt % crosslinkedpolyester and about 1.5 wt % of the inversely synthesized aliphaticpolyurethane particles dispersed therein.

Samples of the above acrylic polymer coated polyester film weresubjected to adhesion, haze value and anti-iridescence appearancetesting. Analytical results shown in Table 3 indicate that theiridescent rating value of 1 to 2 was acceptable to good and adhesionand haze specifications were satisfied.

Comparative Examples 3 and 4

In Comp. Ex. 3, the procedure of Example 2 was repeated except that thecontent of the polyurethane particle in the primer layer was 9.0 wt %.In Comp. Ex. 4, the procedure of Example 2 was again repeated exceptthat the content of the polyurethane particle in the primer layer was0.22 wt %.

Evaluation of Results

Analytical results are shown in Table 3. These examples show thatexcessive amounts of polyurethane particles can detract from opticalclarity of the film (Comp. Ex. 3) and that insufficient polyurethaneparticles do not provide adequate iridescence canceling power (Comp. Ex.4).

Comparative Example 5

The procedure of Example 2 was repeated except that primer solution wasdeposited onto the base layer at about 2.8 g/m² rate such that theprimer thickness after drying was 0.2 μm. Analytical results shown inTable 3 indicate that excessive thickness of the primer layer adverselyaffects optical clarity although iridescence was canceled.

Comparative Examples 6 and 7

For Comp. Ex. 6, the procedure of Example 2 was repeated except that aglyoxal crosslinking agent (Freechem® 40□L from Emerald PerformanceMaterials) was substituted for the carbodiimide crosslinking agent.Freechem 40DL is an aqueous solution of ethanedial which containing lessthan 0.2% residual acid. For Comp. Ex. 7 the same procedure as Ex. 2 wasrepeated except that melamine formaldehyde resin crosslinking agent(Cymel® 385 Cytec Industries, Woodland Park, N.J.) replaced thecarbodiimide crosslinking agent. The amounts of crosslinking agent wasthe same as in Example 2. Analytical results are shown in Table 3. Theyreveal that the inversely synthesized aliphatic polyurethane and primerproportions as in Ex. 2 gave satisfactory iridescence and hazeproperties. However, replacement of carbodiimide by other crosslinkingagents gave inferior Spray and Boil adhesion performance.

TABLE 3 Comp. Comp. Comp. Comp. Comp. Comp. Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex.5 Ex. 6 Ex. 7 Spray Adhesion 1 1 1 1 1 2 3 Boil Adhesion 1 1 1 1 1 2 3Tape Adhesion Pass Pass Pass Pass Pass Pass Pass parallel Tape AdhesionPass Pass Pass Pass Pass Pass Pass perpendicular Iridescence 3 1-2 1-2 31-2 1-2 1-2 Haze % 1.37 1.7 3.53 0.85 6.5 1.22 1.35

Examples 8-11

For Examples 8-10, the procedure of Ex. 2 was repeated substantiallyidentically except that 0.40 pph of PMMA particles was charged into theliquid mixture composition for the primer layer in place ofpolyurethane. In Ex. 8 a mixture of 50 wt. % Techpolymer SSX-102 and 50wt. % Techpolymer SSX-104 microspheres was dispersed in the primer layercoating composition. Both of these Techpolymer materiasl from Sekisuiare solid microsphers. SSX-102 particles had a nominal diameter of 2 μm.Mean diameter was 2.51 μm, median diameter was 2.46 μm, standarddeviation of diameter was 0.25 μm and 97.6% of the particles haddiameter between 2.00 and 3.17 μm. SSX-104 particles had a nominaldiameter of 4 μm. Mean diameter was 4.298 μm, median diameter was 4.239μm, standard deviation of diameter was 0.504 μm and 89.4% of theparticles had diameter between 4.00 and 5.04 μm. For Ex. 9, the PMMAparticles were Techpolymer SSX-103DXE and had a nominal diameter of 3μm, however these were hollow microspheres. Mean diameter was 3.17 μm,median diameter was 3.07 μm, standard deviation of diameter was 0.40 μmand 94.7% of the particles had diameter between 2.52 and 4.00 μm. Thusoverall particle sizes for Exs. 8 and 9 were very similar. The maindifference between these examples was the solid particle structure ofEx. 8 compared to hollow sphere structure of Ex. 9. In Ex. 10 the PMMAnominal particles size was 7 μm. Mean diameter was 6.77 μm, mediandiameter was 6.51 μm, standard deviation of diameter was 2.56 μm and59.0% of the particles had diameter between 4.00 μm and 8.00 μm. Themicrospheres were solid and the particle size distribution about themean was slightly broader than in Exs. 8 and 9. In Example 11 the sameaqueous polyurethane dispersion was used again to essentially repeat Ex.2 within the range of experimental accuracy. Resulting samples weretested together with samples of Comp. Ex. 1 for adhesion, haze andiridescence, as above. Additional iridescence testing was performed.Analytical methods are described and results are presented in Table 4below.

Every one of Comp. Ex. 1 and Exs. 8-11 yielded values of 1 (“good”) inthe Spray Test and Boil Test for adhesion and passed the perpendicularand parallel Tape Peel test. Additional iridescence measurements weremade as follows. Rectangular sheet samples 14 cm wide×22.9 cm high (5.5inch×9 inch) of primer coated base layer film from Comp. Ex. 1, Exs.8-11 were taken from positions at the left side (A), center (B) andright side (C) of a single, 6 meter wide web for each example. The threesamples (A, B and C) were coated with an acrylic polymer coat asdescribed above. A 2.5 cm×2.5 cm (1 inch×1 inch) square hole was cut outnear the center of an opaque 21.6×27.9 cm (8.5 inch×11 inch) cardboardsheet to form a mask. In turn, the mask was laid over the three samplesheets at four observation positions along a corner-to-corner diagonalline of the sheets. The diagonal line was oriented with the sameorientation for all the sheets (i.e., top left corner to bottom rightcorner). The line was divided into five equal length segments and thefour observation positions, OP1-OP4 were located at the interiorjunctions of the segments.

Iridescence assessments and haze measurements were obtained at eachobservation point of the three sheets. Results are shown in Table 4. Theaverage value of iridescence and haze and the standard deviation of thehaze from average were calculated. Results show that the iridescencecanceling with both PMMA (Exs. 8-10) and polyurethane (Ex. 11) in theprimer layer was better than when neither of these materials was present(Comp. Ex. 1). Iridescence canceling performance was very good for thepolyurethane sample and even better for Ex. 8 with nominal 2 μm and 4 μmparticle size, solid PMMA microspheres. Iridescence performance of thelarger solid microspheres of Ex. 10 was less effective but acceptable.Ex. 9 shows that hollow PMMA microspheres had even less effectiveiridescence canceling ability than solid microspheres of about the samesize in Ex. 8. Haze values for all examples were acceptable. For Comp.Ex. 1 this can be attributed to the absence of light scatteringparticles that could increase haze if present as in the operativeexamples. The combination of haze with the small PMMA iridescencereducing particles in Ex. 8 was excellent with an average of 1.50% and avery uniform performance over the areas of samples tested. All of thePMMA samples demonstrated that the microspheres did not significantlydegrade optical clarity although the variability in haze value for thehollow microspheres was the highest of the PMMA samples. The combinationof iridescence and haze analyses suggest that smaller and solid PMMAmicrospheres perform better than hollow microspheres. Ex. 11 withpolyurethane particles also had acceptable haze but was more hazy andhad higher haze variability than all other examples.

Samples of Comp. Ex. 1, Ex. 8 and Ex. 11 were subjected to totalhemispherical reflectance analysis using a Hitachi high technologyU-3900-H UV-Vis-NIR Spectrophotometer. The instrument was set up intotal hemispherical reflectance geometry (8°/t) using a high technology60 mm integrating sphere accessory with the measurement beam focused atthe center of the sphere. The reflectance factor measurements wererelative to barium sulfate instrument calibration standard materialE259-98 and CIE 15.2 at ambient temperature (22°±1° C.). The calibrationof the sample was performed at 1.0 nm intervals over the wavelengthrange from 250 nm to 900 nm for 8°/hemispherical geometry. In the250-320 nm wavelength range a deuterium source was used. Atungsten-halogen source was used in the 340-900 nm wavelength range. Aphotomultiplier detector in the UV-Vis (ultraviolet-visual wavelengthrange) and a lead sulfide detector in the NIR (near infrared wavelengthrange) were also used. Other settings for these analyses were:integrating sphere 60 mm diameter, data mode % reflectance (R), scanspeed 300 nm/min., delay 0 second, cycle time 0 min., auto zero beforeeach run off, PMT voltage auto, slit width 4 nm, lamp change mode auto,base line correction user1, high resolution off, D2 lamp on, WI lamp onand R/S on. Spectral scans were obtained with each sample in 0° and 90°(mutually orthogonal) orientations and the arithmetical average of thetwo analyses were used for plots of results.

Plots of % R vs. wavelength λ (nm) obtained from the hemisphericalreflectance analysis are shown in FIG. 3. The visible wavelengthspectrum extends from about 390 to 750 nm. FIG. 3 shows that for Comp.Ex. 1, % R fluctuates significantly in the visible wavelength range andthus iridescence is significant. Ex. 11 utilized particles of inverselysynthesized polyurethane as the iridescence reducing agent in theprimer. The reflectance plot shows much less variability of reflectancein the visual range. This indicates that the polyurethane particles werevery effective at reducing iridescence. The plot for Ex. 8 that usedPMMA particles in the primer was extremely constant in the visiblerange. This performance demonstates the superior ability of PMMAparticles to cancel iridescence.

TABLE 4 Comp Ex. 1 Comp Ex. 1 Ex. 8 Ex. 8 Ex. 9 Ex. 9 Ex. 10 Ex. 10 Ex.11 Ex. 11 Iridescence Haze Iridescence Haze Iridescence Haze IridescenceHaze Iridescence Haze Location rating (%) rating (%) rating (%) rating(%) rating (%) A/OP1 2 1.18 1 1.49 3 1.45 3 1.64 1 2.57 A/OP2 3 1.50 21.46 2 1.30 2 1.48 1 2.59 A/OP3 2 1.20 1 1.44 3 1.22 3 1.53 1 2.51 A/OP43 1.49 1 1.48 3 1.46 3 1.46 1 3.00 B/OP1 3 1.32 1 1.42 2 1.39 3 1.49 12.57 B/OP2 2 1.27 1 1.48 3 1.46 2 1.62 2 2.36 B/OP3 3 1.38 2 1.58 2 1.293 1.49 2 2.46 B/OP4 3 1.36 1 1.52 3 1.23 2 1.52 2 2.40 C/OP1 3 1.35 21.52 2 1.21 2 1.45 1 2.55 C/OP2 3 1.36 1 1.51 3 1.47 2 1.66 2 2.44 C/OP33 1.38 1 1.56 2 1.38 1 1.48 2 2.44 C/OP4 3 1.35 1 1.48 3 1.20 2 1.55 12.64 average 2.75 1.35 1.25 1.50 2.58 1.36 2.33 1.53 1.42 2.54 std. dev.0.097 0.046 .108 .072 0.167

Although specific forms of the invention have been selected in thepreceding disclosure for illustration in specific terms for the purposeof describing these forms of the invention fully and amply for one ofaverage skill in the pertinent art, it should be understood that varioussubstitutions and modifications which bring about substantiallyequivalent or superior results and/or performance are deemed to bewithin the scope and spirit of the following claims. The entiredisclosure of the US patents and patent applications referred in thisapplication are hereby incorporated herein by reference.

What is claimed is:
 1. A composite film comprising (a) a core layer ofsubstantially particle-free and optically clear polyester, (b) a firstouter layer in direct contact with one side of the core layer, (c) anoptically clear primer layer in direct contact with a side of the firstouter layer opposite the core layer, and (d) optionally, a second outerlayer in direct contact with a side of the core layer opposite the firstouter layer, in which each outer layer is optically clear, isindependently about 0.1 μm-5 μm thick and independently comprisesinorganic particles dispersed uniformly in a polyester matrix, and inwhich the primer layer comprises an iridescence reducing agent selectedfrom the group consisting of inversely synthesized aliphaticpolyurethane particles and polymethylmethacrylate particles uniformlydispersed in a matrix of polyester crosslinked by a carbodiimidecrosslinking agent.
 2. The composite film of claim 1 in which theiridescence reducing agent is polymethylmethacrylate particles.
 3. Thecomposite film of claim 2 in which both of the first outer layer and thesecond outer layer are present.
 4. The composite of claim 2 whichfurther comprises an optically clear protective layer in direct contactwith a side of the primer layer opposite the first outer layer.
 5. Thecomposite of claim 4 in which the protective layer comprises greaterthan 50 wt. % of an acrylic polymer.
 6. The composite of claim 5 inwhich the protective layer is a devolatized residue of a solution of theacrylic polymer dissolved in an organic solvent from which solution theorganic solvent has been substantially removed.
 7. The composite ofclaim 6 in which the protective layer comprises a trace amount of theorganic solvent.
 8. The composite of claim 7 in which the organicsolvent is methyl ethyl ketone.
 9. The composite of claim 6 in which thepolymethylmethacrylate particles are present in the primer layer at aconcentration such that the composite exhibits haze of at most about 3%.10. The composite of claim 9 in which thickness of the primer layer isabout 0.03-0.15 μm.
 11. The composite of claim 4 which is substantiallynon-iridescent under fluorescent illumination.
 12. The composite ofclaim 2 in which the polymethylmethacrylate particles are microspheresof diameter in the range of about 1 μm-10 μm.
 13. The composite of claim12 in which polymethylmethacrylate particles are solid microspheres. 14.The composite of claim 12 in which polymethylmethacrylate particles havea particle size distribution defining a median particle size and theparticle size distribution is narrow such that at least 80 wt. % of theparticles have a diameter within a range from about +4 μm to −4 μm ofthe median particle size.
 15. A method of making an optically clearnon-iridescent composite film comprising the steps of (A) providing amixture comprising an iridescence reducing agent selected from the groupconsisting of inversely synthesized aliphatic polyurethane particles andpolymethylmethacrylate particles and polyester binder particles of apolyester resin having a softening point lower than 100° C. uniformlydispersed in a predominantly aqueous medium comprising carbodiimidecrosslinking agent dissolved in water, (B) providing a base layercomprising a core layer of polyester film of thickness in the range ofabout 1-500 μm and optionally comprising about 0.1 to 2 wt % of a UVlight absorber composition, (C) depositing a wet coating of the mixtureonto one side of the base layer, (D) heating the base layer and wetcoating effectively to (i) soften the polyester binder, (ii) evaporatesubstantially all volatile components of the predominantly aqueousmedium, and (iii), and activate the crosslinking agent, thereby creatingan optically clear film of solidified primer layer in contact with theone side of the base layer, in which the wet coating on the base layeris present in an amount effective to produce a thickness of thesolidified primer layer in the range of about 0.03-0.15 μm.
 16. Themethod of claim 15 in which the iridescence reducing agent ispolymethylmethacrylate particles.
 17. The method of claim 16 in whichthe polymethylmethacrylate particles are present in the primer layer ata concentration effective to make the optically clear non-iridescentcomposite film have a haze value of at most about 3%.
 18. The method ofclaim 16 in which the step of providing the base layer further comprisesthe step of providing a first outer layer about 0.1-5 μm thick andcomprising inorganic particles uniformly dispersed in a polyestermatrix, in which the first outer layer is in direct contact with a sideof the core layer opposite the one side of the base layer bearing theprimer layer, such that the core layer and the first outer layercollectively define the base layer.
 19. The method of claim 18 in whichthe step of providing the base layer further comprises the step ofproviding a second outer layer about 0.1-5 μm thick and optionallycomprising inorganic particles uniformly dispersed in a polyestermatrix, in which the second outer layer is in direct contact with a sideof the core layer opposite the first outer layer, such that the corelayer, first outer layer and second outer layer collectively define thebase layer.
 20. The method of claim 18 which further comprises the stepsof (E) providing a solution comprising acrylic polymer, a cureinitiator, and an amount of organic solvent effective to dissolve theacrylic polymer, (F) placing a uniformly thick solvent-wet coating ofthe solution onto a side of the primer layer opposite the base layer,(G) heating solvent-wet coating effectively to evaporate substantiallyall volatile components of the organic solvent, thereby creating anoptically clear film having a protective layer of solidified acrylicpolymer in contact with the primer layer, in which acrylic polymercomprises greater than 50 wt. % of the primer layer.
 21. The method ofclaim 19 in which the protective layer is effective to make theoptically clear non-iridescent composite film have a haze value of atmost about 3%.
 22. The method of claim 16 in which thepolymethylmethacrylate particles are microspheres of diameter in therange of about 1 μm to about 10 μm and in which polymethylmethacrylateparticles have a particle size distribution defining a median particlesize and the particle size distribution is narrow such that at least 80wt. % of the particles have a diameter within a range from about +4 μmto −4 μm of the median particle size.